A novel migratory dynamic kinetic resolution based on the interplay between an enzyme acylation catalyst and a heterogeneous Brønsted acid as an isomerization/racemization catalyst gives rise to carbocyclic allylic esters with excellent stereoselectivity from readily available tertiary carbinols. An easy-to-use teabag setup combining resin-bound catalysts, a biphasic isooctane–water solvent system, and a highly lipophilic acyl donor efficiently suppresses side reactions and allows for the preparation of functionalized carbocyclic building blocks in high yields and optical purity.

The combination of an enzyme-mediated enantioselective desymmetrization of readily available 3-benzyloxyglutarates and subsequent rhodium-catalyzed oxonium ylide rearrangement of their corresponding in situ derived diazo ketones offers a very concise and highly stereoselective access to functionalized tetrahydrofuranone building blocks.

The first asymmetric total synthesis of hyperiones A and B, two norlignans from Hypericum chinense, has been accomplished following a chemoenzymatic approach. Key features of this synthesis include the lipase-catalyzed enantioselective desymmetrization of a prochiral allenic diol and a silver-mediated cycloisomerization of the resulting axially chiral product to furnish the furan core structure. Two alternative pathways, a ruthenium-catalyzed redox isomerization on the one side and a platinum-catalyzed hydrogenation on the other, are described to finally obtain the desired norlignans.

The implementation of lipase catalysis as a tool for the preparation of optically active biaryls is discussed. While attempts toward dynamic kinetic resolution based on the catalytic ring opening of configurationally unstable biaryl lactones were fruitless, kinetic resolution via transesterification of hydroxymethyl-decorated substrates was successfully employed in the generation of optically enriched, axially chiral biaryls.(P)-1-(2-Hydroxy-4,6-dimethylphenyl)-2-(hydroxymethyl)naphthaleneC19H18O2Ee = 79% from HPLC[α]D20=+21.9 (c 0.8, CHCl3)Source of chirality: Lipase from M. mieheiAbsolute configuration: (P) (assignment by comparison of the specific rotation with literature data)(P)-1-(2-Hydroxy-3,6-dimethylphenyl)-2-(hydroxymethyl)naphthaleneC19H18O2Ee = 87% from HPLC[α]D20=+27.2 (c 0.4, CHCl3)Source of chirality: Lipase from M. mieheiAbsolute configuration: (P) (assignment by comparison of the specific rotation with literature data of analogous compounds)

The first asymmetric total synthesis of hyperiones A and B, two norlignans from Hypericum chinense, has been accomplished following a chemoenzymatic approach. Key features of this synthesis include the lipase-catalyzed enantioselective desymmetrization of a prochiral allenic diol and a silver-mediated cycloisomerization of the resulting axially chiral product to furnish the furan core structure. Two alternative pathways, a ruthenium-catalyzed redox isomerization on the one side and a platinum-catalyzed hydrogenation on the other, are described to finally obtain the desired norlignans.